CN110496613B - Hydrogenation catalyst, preparation method thereof and method for preparing o-diaminomethylcyclohexane - Google Patents
Hydrogenation catalyst, preparation method thereof and method for preparing o-diaminomethylcyclohexane Download PDFInfo
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- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
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Abstract
The invention discloses a hydrogenation catalyst, a preparation method thereof and a method for preparing o-diaminomethylcyclohexane. The carrier of the catalyst is gamma-Al2O3And Mg2The active components of the Si composite carrier are NiO and CuS. The catalyst can be applied to the hydrogenation of o-diaminotoluene to prepare o-diaminomethylcyclohexane, and has the advantages of high activity, high selectivity and high stability. The conversion rate of raw materials is 100 percent, the product yield is more than 98 percent, and the selectivity of deamination products and secondary amine products can be inhibited. The catalyst can run for a long period of 5000h, and the activity of the catalyst is basically unchanged, so that the production cost is greatly reduced.
Description
Technical Field
The invention relates to a hydrogenation catalyst, in particular to a catalyst for preparing o-diaminomethylcyclohexane and a preparation method thereof, and a method for preparing o-diaminomethylcyclohexane by hydrogenation.
Background
Ortho-diaminomethylcyclohexanes such as 1, 2-diaminomethylcyclohexane, i.e. 1, 2-diamino-3-methylcyclohexane and 1, 2-diamino-4-methylcyclohexane, are important raw materials, in particular hardeners (crosslinking agents) for producing epoxy resins.
The catalytic hydrogenation of aromatic amines to diaminomethylcyclohexane is known, with rhodium, ruthenium, nickel and cobalt being widely used hydrogenation catalysts. The main problem of the hydrogenation of aromatic amine compounds is the service life of the catalyst, the aromatic amine is difficult to hydrogenate, and various impurities in the raw material of the aromatic amine often cause the inactivation of the catalyst.
US3450759 discloses a process for the preparation of diaminomethylcyclohexane by the catalytic hydrogenation of toluenediamine, which teaches that the conversion of the starting material and the yield of the product are low due to the presence of small amounts of o-toluenediamine impurities. To achieve complete hydrogenation of the toluene diamine, it is generally necessary to remove the ortho-toluene diamine from the feedstock prior to hydrogenation.
US6429338 discloses a process for the catalytic hydrogenation of monocyclic aromatic diamines to produce cyclohexylamines. This patent uses rhodium/alumina as catalyst, C4-12Dialkyl ether is used as a solvent, o-toluenediamine is slowly added into the high-pressure kettle in a semi-continuous mode in the hydrogenation process, and the contact time of the o-toluenediamine and the catalyst in the raw materials is minimized by controlling the feed rate to be matched with the hydrogenation rate, so that the purpose of reducing the deactivation rate of the catalyst is achieved. However, the patent has the problems of low raw material concentration and difficult control of the reaction process.
US2009253938 discloses a process for the preparation of 1, 2-diamino-3-methylcyclohexane and/or 1, 2-diamino-4-methylcyclohexane which uses rhodium/alumina as catalyst, a mixture of dialkyl and/or alicyclic ethers as solvent, and achieves high conversion of the feedstock by a combination of ammonia and lithium hydroxide additive. Meanwhile, the patent states that even at a high o-tolylenediamine concentration, the catalyst remains active and stable, but the patent has problems of low product selectivity, and also, the use of a large amount of liquid ammonia during the reaction has problems of resource waste and environmental pollution.
In the prior art, the process for preparing diaminomethylcyclohexane by catalytic hydrogenation of o-toluenediamine has the following problems:
(1) the existing catalytic hydrogenation process has harsh conditions, and the deamination product and secondary amine in the product have high content, so that the product has poor selectivity and low quality;
(2) the intermittent process is adopted, so that the influence factors are more, the product quality is unstable, and meanwhile, the concentration of a raw material substrate in the reaction process is low, so that the method is not suitable for large-scale continuous industrial production;
(3) the method adopts a large amount of volatile ether solvents, and has the problems of difficult solvent recovery and environmental pollution.
Therefore, there is a need to find a catalyst that can fundamentally solve the problems of catalyst activity, selectivity and stability, and simultaneously achieve the purposes of improving production efficiency and product quality and reducing environmental pollution by continuously optimizing process conditions.
Disclosure of Invention
It is an object of the present invention to provide a hydrogenation catalyst. By introducing another active component CuS into the Ni-containing active component, the activity and stability of the catalyst are greatly improved, and meanwhile, Mg in the carrier2The introduction of Si can effectively prevent the strong interaction between the metal active component and the carrier, avoid the active component from forming a spinel phase, further improve the activity of the catalyst and on the other hand Mg2The introduction of Si can greatly improve the selectivity of the product.
Another aspect of the present invention is to provide a method for preparing the above catalyst, which is simple in process.
It is a further object of the present invention to provide a process for preparing o-diaminomethylcyclohexane using the above catalyst.
In order to realize the purpose, the invention adopts the following technical scheme:
catalyst for preparing o-diaminomethylcyclohexane with gamma-Al as carrier2O3And Mg2The active components of the Si composite carrier are NiO and CuS.
The carrier of the invention is gamma-Al2O3Specific surface area of 150-300m2Per g, preferably 200-240m2/g。
Mg of the present invention2Specific surface area of Si 100-2G, preferably 130-160m2/g。
Mg in the vector of the present invention2The content of Si is 10-20wt%, gamma-Al2O3In an amount of 80 to 90 wt.%, preferably Mg2The content of Si is 12-18wt%, gamma-Al2O3Is present in an amount of 82 to 88 wt.%, based on the weight of the support.
The catalyst of the invention comprises the following active components: based on the weight of the carrier,
the content of NiO is 1 to 15wt%, preferably 5 to 10 wt%;
the content of CuS is 0.1-5 wt.%, preferably 0.5-2.5 wt.%.
The preparation method of the catalyst comprises the following steps: according to the proportion,
1) to gamma-Al2O3And Mg2Adding CuS, peptizing agent, binder and extrusion aid into Si, uniformly mixing, adding deionized water, kneading into a plastic block, extruding and molding the block by using an extrusion machine, drying and roasting to obtain a semi-finished catalyst;
2) and (3) impregnating the semi-finished catalyst with a metal nickel salt aqueous solution, preferably impregnating in an equal volume, and drying and roasting after the impregnation is finished to obtain the catalyst precursor.
The peptizing agent in step 1) of the present invention is selected from nitric acid, acetic acid, boric acid, citric acid or tartaric acid, preferably citric acid.
The binder in step 1) of the present invention is selected from methylcellulose, polyvinyl alcohol, polypropylene or soluble starch, preferably methylcellulose.
The extrusion aid in the step 1) is preferably sesbania powder.
The peptizing agent in step 1) of the present invention is used in an amount of 1 to 5wt%, preferably 2 to 4wt%, based on γ -Al2O3And Mg2The sum of Si weights.
The binder used in step 1) of the present invention is used in an amount of 0.5 to 2wt%, preferably 1 to 1.5wt%, based on γ -Al2O3And Mg2The sum of Si weights.
The dosage of the extrusion aid in the step 1) of the invention is1 to 3 wt.%, preferably 1.5 to 2.5 wt.%, based on γ -Al2O3And Mg2The sum of Si weights.
The metallic nickel salt in the step (2) of the present invention is selected from one or more of nickel sulfate, nickel nitrate and nickel acetate, and is preferably nickel nitrate.
The drying temperature of the step 1) is 80-120 ℃, the drying time is 3-7 h, the preferred drying temperature is 100-110 ℃, and the drying time is 4-6 h.
The roasting temperature of the step 1) is 200-400 ℃, the roasting time is 4-10 h, the preferred roasting temperature is 240-350 ℃, and the roasting time is 6-8 h.
The semi-finished catalyst product obtained in the step 1) is cylindrical, clover, seven-hole spherical, gear-shaped or plum blossom-shaped, and preferably clover.
The drying temperature of the step 2) is 100-150 ℃, the drying time is 4-10 h, the preferable drying temperature is 120-140 ℃, and the drying time is 6-9 h; the roasting temperature is 300-500 ℃, the roasting time is 6-10h, the preferred roasting temperature is 400-450 ℃, and the roasting time is 7-9 h.
The catalyst of the invention is suitable for preparing o-diaminomethylcyclohexane by catalytic hydrogenation of o-diaminotoluene. Namely: the catalyst of the invention is suitable for preparing 1, 2-diamino-3-methylcyclohexane by catalytic hydrogenation of 2, 3-diaminotoluene. The catalyst of the invention is also suitable for preparing 1, 2-diamino-4-methylcyclohexane by catalytic hydrogenation of 3, 4-diaminotoluene.
The catalyst of the invention needs to have hydrogenation activity after being activated. The activation method comprises the following steps: at normal pressure, the reduction is carried out for 4-12h, preferably 6-10h at 200-500 ℃, preferably 300-400 ℃ in a pure hydrogen atmosphere.
A method for preparing o-diaminomethylcyclohexane by catalytic hydrogenation of o-diaminotoluene comprises the following steps: adopting a continuous fixed bed process, wherein the space velocity is 1-10L/h/L Cat, and preferably 3-8L/h/L Cat; the molar ratio of hydrogen to ortho-diaminotoluene was 3: 1-10: 1, preferably 5: 1-8: 1; the reaction temperature is 80-200 ℃, and preferably 110-160 ℃; the catalytic hydrogenation reaction is carried out under the condition that the absolute reaction pressure is 3.0-15.0 MPa, and preferably 5.0-10.0 MPa.
The invention has the beneficial effects that:
(1) the catalyst carrier and the active components adopted in the preparation method are easy to obtain, and the catalyst has simple preparation process, easy large-scale preparation and low investment cost.
(2) In the research process of the invention, the addition of CuS is surprisingly found out, so that on one hand, the active metal is more uniformly dispersed on the surface of the composite carrier, and the stability of the micro-morphology of the nickel active site on the composite carrier can be maintained, thereby greatly improving the activity of the catalyst; on the other hand, the chelation between the o-diaminotoluene and the active metal Ni is effectively reduced, so that the irreversible inactivation of the catalyst caused by the chelation is avoided, and the stability of the catalyst is greatly improved. The catalyst of the invention is used for catalyzing hydrogenation reaction of o-diaminotoluene, the service cycle of the catalyst can be prolonged from 100h to more than 5000h, and the activity of the catalyst is basically unchanged, thereby greatly reducing the production cost.
(3) The invention adopts gamma-Al2O3And Mg2Si composite carrier, Mg2The introduction of Si can effectively prevent strong interaction between the metal active component and the carrier, avoid the active component from forming a spinel phase, and further improve the activity of the catalyst2Si can greatly inhibit the generation of deamination products and secondary amine products, when Mg2When the content of Si is less than 10wt% or more than 20wt%, the yield of deamination product and secondary amine product in the product is increased to more than 5wt%, and when Mg is contained2The content of Si is within 10-20wt%, the yield of deamination products and secondary amine products in the product is reduced to below 1%, and the yield of the product is stabilized to above 98%.
(4) The invention adopts a continuous production process, has mild reaction conditions, less side reactions, stable product quality, good economy and good application prospect.
(5) The invention adopts a solvent-free process, has high production efficiency and thoroughly solves the problems of solvent recovery and environmental pollution.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples listed, and it should also include equivalent modifications and variations to the technical solutions defined in the claims appended to the present application.
Gas chromatograph: shimadzu GC-2014(FID) detector, SE-30 capillary column
The sample inlet is 280 ℃, and the detector is 300 ℃; temperature rising procedure: keeping the temperature at 50 deg.C for 2min, and raising the temperature to 260 deg.C at 40 deg.C/min for 10 min.
In the examples, the hydrogenation reactor is a fixed bed reactor.
γ-Al2O3: purchased in a Zibo Ziziruifeng factory with the specific surface area of 220m2/g。
Mg2Si: a specific surface area of 150m, available from brocade Metal materials Co., Ltd, of Dongguan2/g。
Example 1
(1)1％NiO-0.1％CuS/80％Al2O3-20％Mg2Preparation of Si catalyst
To 80g of gamma-Al2O3And 20g Mg2Adding 0.1g of CuS, 1g of citric acid, 2g of methylcellulose and 1g of sesbania powder into Si, uniformly mixing, adding 5.0g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruding machine, drying at 100 ℃ for 5 hours, and roasting at 260 ℃ for 5 hours to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into the catalyst containing 3.89g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying the mixture for 10h at 100 ℃, and roasting the dried mixture for 6h at 500 ℃ to obtain the catalyst precursor of 1 percent NiO-0.1 percent CuS/80 percent Al2O3-20％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 6 hours at 300 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 110 ℃, the pressure is increased to 5.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 10L/h/L Cat, hydrogen with the molar weight being 3 times of that of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 99.4 percent, the yield of deamination products in the product is 0.2 percent, and the yield of secondary amine products is 0.4 percent through gas chromatography analysis. The catalyst is continuously operated for 6000h, sampling and analyzing are carried out, the reaction conversion rate is 99.2%, the product yield is 98.7%, the deamination product yield in the product is 0.2%, and the secondary amine product yield is 0.3%.
Comparative example 1
(1)1％NiO/80％Al2O3-20％Mg2Preparation of Si catalyst
To 80g of gamma-Al2O3And 20g Mg2Adding 1g of citric acid, 2g of methylcellulose and 1g of sesbania powder into Si, uniformly mixing, adding 5.0g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruder, drying at 100 ℃ for 5 hours, and roasting at 260 ℃ for 5 hours to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into the catalyst containing 3.89g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying the mixture for 10h at 100 ℃, and roasting the dried mixture for 6h at 500 ℃ to obtain the catalyst precursor of 1 percent NiO/80 percent Al2O3-20％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 6 hours at 300 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 110 ℃, the pressure is increased to 5.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 10L/h/L Cat, hydrogen with the molar weight being 3 times of that of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 90.0 percent, the product yield is 89.3 percent, the yield of deamination products in the product is 0.4 percent, and the yield of secondary amine products is 0.3 percent through gas chromatography analysis. The catalyst is continuously operated for 100 hours, sampling and analyzing are carried out, the reaction conversion rate is 70.0 percent, the product yield is 69.3 percent, the deamination product yield in the product is 0.6 percent, and the secondary amine product yield is 0.1 percent.
Comparative example 2
(1)1％NiO-0.1％CuS/91％Al2O3-9％Mg2Preparation of Si catalyst
To 91g of gamma-Al2O3And 9g Mg2Adding 0.1g of CuS, 1g of citric acid, 2g of methylcellulose and 1g of sesbania powder into Si, uniformly mixing, adding 5.0g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruding machine, drying at 100 ℃ for 5 hours, and roasting at 260 ℃ for 5 hours to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into the catalyst containing 3.89g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying the mixture for 10h at 100 ℃, and roasting the dried mixture for 6h at 500 ℃ to obtain the catalyst precursor of 1 percent NiO-0.1 percent CuS/91 percent Al2O3-9％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 6 hours at 300 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 110 ℃, the pressure is increased to 5.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 10L/h/L Cat, hydrogen with the molar weight being 3 times of that of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 91.5 percent, the yield of deamination products in the product is 3.5 percent, and the yield of secondary amine products is 5.0 percent through gas chromatography analysis. The catalyst is continuously operated for 6000h, sampling and analysis are carried out, the reaction conversion rate is 95.0%, the product yield is 80.7%, the deamination product yield in the product is 5.8%, and the secondary amine product yield is 8.5%.
Comparative example 3
(1)1％NiO-0.1％CuS/79％Al2O3-21％Mg2Preparation of Si catalyst
To 79g of gamma-Al2O3And 21g Mg2Adding 0.1g of CuS, 1g of citric acid, 2g of methylcellulose and 1g of sesbania powder into Si, uniformly mixing, adding 5.0g of deionized water, kneading into a plastic block, and extruding the block by using a strip extruding machineExtruding the mixture into clover shape, drying at 100 deg.C for 5 hr, and calcining at 260 deg.C for 5 hr to obtain semi-finished catalyst.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into the catalyst containing 3.89g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying the mixture for 10h at 100 ℃, and roasting the dried mixture for 6h at 500 ℃ to obtain the catalyst precursor of 1 percent NiO-0.1 percent CuS/79 percent Al2O3-21％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 6 hours at 300 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 110 ℃, the pressure is increased to 5.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 10L/h/L Cat, hydrogen with the molar weight being 3 times of that of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 87.0 percent, the yield of deamination products in the product is 5.6 percent, and the yield of secondary amine products is 7.4 percent through gas chromatography analysis. The catalyst continuously runs for 6200h, and sampling analysis shows that the reaction conversion rate is 92.0%, the product yield is 73.8%, the deamination product yield in the product is 8.0%, and the secondary amine product yield is 10.2%.
Comparative example 4
(1)1％NiO-0.1％CuS/80％Al2O3Preparation of-20% LiOH catalyst
To 80g of gamma-Al2O3And 20g of LiOH, adding 0.1g of CuS, 1g of citric acid, 2g of methylcellulose and 1g of sesbania powder, uniformly mixing, adding 5.0g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruding machine, drying at 100 ℃ for 5h, and roasting at 260 ℃ for 5h to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into the catalyst containing 3.89g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying the mixture for 10h at 100 ℃, and roasting the dried mixture for 6h at 500 ℃ to obtain the catalyst precursor of 1 percent NiO-0.1 percent CuS/80 percent Al2O3-20％LiOH。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 6 hours at 300 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 110 ℃, the pressure is increased to 5.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 10L/h/L Cat, hydrogen with the molar weight being 3 times of that of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 94.0 percent, the product yield is 86.9 percent, the yield of deamination products in the product is 2.5 percent, and the yield of secondary amine products is 4.6 percent through gas chromatography analysis. The catalyst is continuously operated for 5500h, sampling and analyzing are carried out, the reaction conversion rate is 85.0 percent, the product yield is 72.0 percent, the deamination product yield in the product is 5.4 percent, and the secondary amine product yield is 7.6 percent.
Comparative example 5
The evaluation was carried out using a 4% Rh/alumina catalyst of the prior art.
The catalyst evaluation was carried out by a continuous fixed bed process. The temperature in the reactor is maintained at 110 ℃, the pressure is increased to 5.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 10L/h/L Cat, hydrogen with the molar weight being 3 times of that of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 90.5 percent, the product yield is 79.6 percent, the yield of deamination products in the product is 5.2 percent, and the yield of secondary amine products is 5.7 percent through gas chromatography analysis. The catalyst is continuously operated for 100 hours, sampling and analysis are carried out, the reaction conversion rate is 65.0 percent, the product yield is 46.2 percent, the deamination product yield in the product is 10.2 percent, and the secondary amine product yield is 8.6 percent.
Example 2
(1)5％NiO-5％CuS/82％Al2O3-18％Mg2Preparation of Si catalyst
To 82g of gamma-Al2O3And 18g Mg2Adding 5g of CuS, 2g of citric acid, 1.5g of methylcellulose and 1.5g of sesbania powder into Si, uniformly mixing, adding 6g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruding machine, drying at 80 ℃ for 6h, and roasting at 300 ℃ for 4h to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, adopting equal-volume impregnationBy immersing the semi-finished catalyst in a bath containing 19.47g of Ni (NO)3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying the mixture for 9h at 115 ℃, roasting the dried mixture for 7h at 450 ℃ to obtain the catalyst precursor of 5 percent NiO-5 percent CuS/82 percent Al2O3-18％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 12 hours at 200 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 110 ℃, the pressure is increased to 5.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 8L/h/L Cat, hydrogen with 5 times of the molar weight of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 99.3 percent, the yield of deamination products in the product is 0.3 percent, and the yield of secondary amine products is 0.4 percent through gas chromatography analysis. The catalyst is continuously operated for 5500h, sampling and analyzing are carried out, the reaction conversion rate is 99.0%, the product yield is 98.4%, the deamination product yield in the product is 0.4%, and the secondary amine product yield is 0.2%.
Example 3
(1)8％NiO-0.5％CuS/84％Al2O3-16％Mg2Preparation of Si catalyst
To 84g of gamma-Al2O3And 16g Mg2Adding 0.5g of CuS, 3g of citric acid, 1g of methylcellulose and 2g of sesbania powder into Si, uniformly mixing, adding 7g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruding machine, drying at 90 ℃ for 4 hours, and roasting at 240 ℃ for 6 hours to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into the catalyst containing 31.15g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying the mixture for 8 hours at the temperature of 120 ℃, and roasting the dried mixture for 8 hours at the temperature of 400 ℃ to obtain the catalyst precursor of 8 percent NiO-0.5 percent CuS/84 percent Al2O3-16％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 10 hours at 350 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 130 ℃, the pressure is increased to 7.0MPa, after the system is stable, 2, 3-diaminotoluene is pumped into the reactor at the airspeed of 5L/h/L Cat, hydrogen with the molar weight 7 times that of the 2, 3-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 99.2 percent, the yield of deamination products in the product is 0.5 percent, and the yield of secondary amine products is 0.3 percent through gas chromatography analysis. 7000h sampling analysis is carried out on the catalyst continuously, the reaction conversion rate is 98.9%, the product yield is 98.2%, the deamination product yield in the product is 0.4%, and the secondary amine product yield is 0.3%.
Example 4
(1)10％NiO-1％CuS/86％Al2O3-14％Mg2Preparation of Si catalyst
To 86g of gamma-Al2O3And 14g Mg2Adding 1g of CuS, 4g of citric acid, 0.5g of methylcellulose and 2.5g of sesbania powder into Si, uniformly mixing, adding 8g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruding machine, drying at 120 ℃ for 5 hours, and roasting at 200 ℃ for 8 hours to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into a catalyst containing 38.93g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying for 7h at 130 ℃, and roasting for 9h at 350 ℃ to obtain the catalyst precursor of 10 percent NiO-1 percent CuS/86 percent Al2O3-14％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 8 hours at 400 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 150 ℃, the pressure is increased to 8.0MPa, after the system is stable, 3, 4-diaminotoluene is pumped into the reactor at the airspeed of 7L/h/L Cat, hydrogen with the molar weight 8 times that of 3, 4-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 99.4 percent, the yield of deamination products in the product is 0.3 percent, and the yield of secondary amine products is 0.3 percent through gas chromatography analysis. The catalyst is continuously operated for 6500h, sampling and analyzing, the reaction conversion rate is 98.5%, the product yield is 98.0%, the deamination product yield in the product is 0.2%, and the secondary amine product yield is 0.3%.
Example 5
(1)12％NiO-1.5％CuS/88％Al2O3-12％Mg2Preparation of Si catalyst
To 88g of gamma-Al2O3And 12g Mg2Adding 1.5g of CuS, 2.5g of citric acid, 1.8g of methylcellulose and 3.0g of sesbania powder into Si, uniformly mixing, adding 9g of deionized water, kneading into a plastic block, extruding the block into a clover shape by using an extruding machine, drying at 110 ℃ for 7h, and roasting at 400 ℃ for 9h to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into the catalyst containing 46.72g of Ni (NO) by an equal volume impregnation method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying for 6h at 140 ℃, and roasting for 10h at 300 ℃ to obtain the catalyst precursor of 12 percent NiO-1.5 percent CuS/88 percent Al2O3-12％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 7h at 450 ℃ in a hydrogen stream (under normal pressure). The temperature in the reactor is maintained at 160 ℃, the pressure is increased to 10.0MPa, after the system is stable, 3, 4-diaminotoluene is pumped into the reactor at the airspeed of 3L/h/L Cat, hydrogen with the molar weight 9 times that of the 3, 4-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 99.1 percent, the yield of deamination products in the product is 0.2 percent, and the yield of secondary amine products is 0.7 percent through gas chromatography analysis. The catalyst is continuously operated for 7500h, sampling and analyzing, the reaction conversion rate is 98.6%, the product yield is 98.2%, the deamination product yield in the product is 0.1%, and the secondary amine product yield is 0.3%.
Example 6
(1)15％NiO-2.5％CuS/90％Al2O3-10％Mg2Preparation of Si catalyst
To 90g of gamma-Al2O3And 10g Mg2Adding 2.5g of CuS, 5g of citric acid, 0.6g of methylcellulose and 1.8g of sesbania powder into Si, uniformly mixing, and addingKneading 10g of deionized water into a plastic block, extruding the block into a clover shape by a strip extruder, drying at 105 ℃ for 3h, and roasting at 350 ℃ for 10h to obtain a semi-finished catalyst for later use.
According to the content composition of the catalyst, the semi-finished catalyst is immersed into a catalyst containing 58.40g of Ni (NO) by an equal volume immersion method3)3·6H2In 100ml of O aqueous solution, after the adsorption is balanced, drying for 4h at 150 ℃, and roasting for 8h at 420 ℃ to obtain the catalyst precursor of 15 percent NiO-2.5 percent CuS/90 percent Al2O3-10％Mg2Si。
(2) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 4 hours at 500 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is maintained at 200 ℃, the pressure is increased to 3.0MPa, after the system is stable, 3, 4-diaminotoluene is pumped into the reactor at the airspeed of 1L/h/L Cat, hydrogen with the molar weight being 10 times that of the 3, 4-diaminotoluene is introduced, and the reaction conversion rate is 100.0 percent, the product yield is 99.5 percent, the yield of deamination products in the product is 0.3 percent, and the yield of secondary amine products is 0.2 percent through gas chromatography analysis. The catalyst is continuously operated for 8000h, and is sampled and analyzed, the reaction conversion rate is 98.7%, the product yield is 98.3%, the deamination product yield in the product is 0.2%, and the secondary amine product yield is 0.2%.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes or modifications of the technical solution of the present invention are within the spirit of the present invention.
Claims (15)
1. A hydrogenation catalyst with gamma-Al as carrier2O3And Mg2The Si composite carrier comprises NiO and CuS as active components; mg in the carrier2The content of Si is 10-20wt%, gamma-Al2O3The content of (B) is 80-90wt%Based on the weight of the carrier; the active component content of the catalyst is as follows: the content of NiO is 1-15wt% based on the weight of the carrier; the content of CuS is 0.1-5 wt%.
2. The catalyst of claim 1, wherein the γ -Al is2O3Specific surface area of 150-300m2/g；Mg2Specific surface area of Si 100-2/g。
3. The catalyst of claim 1, wherein the γ -Al is2O3Specific surface area of 200-2/g；Mg2Specific surface area of Si 130-160m2/g。
4. The catalyst of claim 1, wherein the support comprises Mg2The content of Si is 12-18wt%, gamma-Al2O3Is present in an amount of 82 to 88 wt.%, based on the weight of the support.
5. The catalyst according to claim 1, characterized in that the active component content of the catalyst is as follows: the content of NiO is 5-10wt% based on the weight of the carrier; the content of CuS is 0.5-2.5 wt%.
6. A process for preparing the catalyst of any one of claims 1-5, comprising the steps of: according to the proportion,
1) to gamma-Al2O3And Mg2Adding CuS, peptizing agent, binder and extrusion aid into Si, uniformly mixing, adding deionized water, kneading into a plastic block, extruding and molding the block by using an extrusion machine, drying and roasting to obtain a semi-finished catalyst;
2) and (3) impregnating the semi-finished catalyst with a metal nickel salt aqueous solution, and drying and roasting after the impregnation is finished to obtain a catalyst precursor.
7. The method as claimed in claim 6, wherein the impregnation in step 2) is an equal volume impregnation.
8. The method of claim 6, wherein the peptizing agent comprises one or more of nitric acid, acetic acid, boric acid, citric acid, and tartaric acid; and/or the binder comprises one or more of methyl cellulose, polyvinyl alcohol, polypropylene and soluble starch; and/or the extrusion aid is sesbania powder.
9. The method of claim 6, wherein the method is based on γ -Al2O3And Mg2Si, wherein the amount of the peptizing agent is 1-5 wt%; and/or the presence of a gas in the gas,
the dosage of the binder is 0.5-2 wt%; and/or the presence of a gas in the gas,
the amount of the extrusion aid is 1-3 wt%.
10. The method of claim 6, wherein the method is based on γ -Al2O3And Mg2Si, wherein the amount of the peptizing agent is 2-4 wt%; and/or the presence of a gas in the gas,
the dosage of the binder is 1-1.5 wt%; and/or the presence of a gas in the gas,
the amount of the extrusion aid is 1.5-2.5 wt%.
11. The method as claimed in claim 6, wherein the roasting temperature of the step 1) is 200-400 ℃, and the roasting time is 4-10 h; and/or, the roasting temperature in the step 2) is 300-500 ℃, and the roasting time is 6-10 h.
12. The method as claimed in claim 6, wherein the roasting temperature of the step 1) is 240-350 ℃, and the roasting time is 6-8 h; and/or, the roasting temperature in the step 2) is 400-450 ℃, and the roasting time is 7-9 h.
13. A method for preparing o-diaminomethylcyclohexane by catalytic hydrogenation of o-diaminotoluene comprises the following steps: preparing 1, 2-diamino-3-methylcyclohexane by catalytic hydrogenation of 2, 3-diaminotoluene with the catalyst of any one of claims 1 to 5; or 3, 4-diaminotoluene is catalyzed and hydrogenated to prepare the 1, 2-diamino-4-methylcyclohexane.
14. The method of claim 13, wherein the method adopts a continuous fixed bed process, and the space velocity is 1-10L/h/L Cat; the molar ratio of hydrogen to ortho-diaminotoluene was 3: 1-10: 1; the reaction temperature is 80-200 ℃; the catalytic hydrogenation reaction is carried out under the condition that the absolute reaction pressure is 3.0-15.0 MPa.
15. The method of claim 13, wherein the method adopts a continuous fixed bed process, and the space velocity is 3-8L/h/L Cat; the molar ratio of hydrogen to ortho-diaminotoluene was 5: 1-8: 1; the reaction temperature is 110-160 ℃; the catalytic hydrogenation reaction is carried out under the condition that the absolute reaction pressure is 5.0-10.0 MPa.
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